High temperature metathesis chemistry

ABSTRACT

A method of carrying out a metathesis reaction includes the combination of at least one alkene or non conjugated diene with a Ruthenium-based catalyst with an cyclic(alkyl)(amino)carbene ligand to form a reaction mixture and heating the reaction mixture to a temperature of 100° C. or greater. The reaction can be an ADMET, ROMP, a metathesis ring-closure or an olefin exchange reaction.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 62/545,504, filed Aug. 15, 2017, titled HIGH TEMPERATUREMETATHESIS CHEMISTRY, which is incorporated by reference herein in itsentirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under W911NF-13-1-0362awarded by the ARMY/ARO. The government has certain rights in thisinvention.

BACKGROUND

Early methods for olefin metathesis or olefin disproportionation wereperformed using ill-defined metathesis catalyst based on group VI andVII transition metals (W, Mo, and Re). The advent of well-definedGrubb's ruthenium type catalysts introduced stability under ambientconditions and functional group tolerance to metathesis chemistry.Olefin metathesis using Grubb's type ruthenium catalysts aretraditionally performed at temperatures ranging from 20 to 60° C.Degradation or olefin migration can be problematic at elevatedtemperatures. Access to elevated reaction temperatures can potentiallyenhance metathesis chemistry by unlocking products previously unrealizeddue to thermodynamic constraints. Metathesis polymerization above thepolymer's melting temperature can benefit by allowing the resultantpolymer chains to remain unconstrained by crystallization to increasechain diffusion and molecular weight during polymerization.

In the case of metathesis polymerization, acyclic diene metathesispolymerization (ADMET) has been shown to be a useful technique forsynthesizing precision functional polyolefin derivatives. The resultantpolymers are highly crystalline, exhibiting high melting temperatures.As a result, the polymers are synthesized in solution or solid state.Both techniques limit efficient step growth polymerization, restrictingthe molecular weight attainable. Additionally, solution polymerizationrequires the application of vacuum during polymerization. Negativepressure is necessary to remove gaseous ethylene and drive themetathesis equilibrium towards polymerization. Weychardt et al.Organometallics, 2008, 27 (7), pp 1479-85 developed a procedure usinghigh boiling point solvents thus light vacuum could be applied. Whilethis method is valuable, solvent purification is required and the use ofsolvent is cumbersome for scale up and industrial process.

Gaines et al. Macromol. Chem. Phys. 2016, 217, 2351-9 demonstratedprecision aliphatic polysulfones synthesized via ADMET. The polymersdisplayed high melting temperature which increased with increasingsulfone content. Both bulk and solution polymerization techniques wereineffective at producing high molecular weight polymer. The high meltingtemperature of the polymer limited polymer molecular weight using bulksynthesis with Grubb's 1^(st) generation catalyst. Raising thepolymerization temperature to above the melting temperature (T_(m)) ofunsaturated polymer product (about 130° C.) degrades the catalyst.Solution polymerization was performed; however, polymer insolubilitylimited the polymer's molecular weight. The polysulfones are a primecandidate for bulk high-temperature metathesis polymerization.

Hence there remains a need for carrying out metathesis reactions attemperatures in excess of 100° C.

BRIEF SUMMARY

Various embodiments are directed to carrying out the metathesis of anolefin, which is an organic molecule with at least one alkene or atleast two non-conjugated ene-groups, using a Ruthenium-based catalyst,such as a Hoveyda-Grubb's type catalyst, comprising an asymmetricN-heterocyclic carbene ligand or a cyclic (alkyl)(amino)carbene ligand(hereinafter, a “Ruthenium-based catalyst”) with heating the reactionmixture to a temperature greater than 100° C. The metathesis can be partof a metathesis polymerization where, in the case of a ring-openingmetathesis polymerisation (ROMP), a cyclic monomer or a combination ofcyclic monomers are converted to a polymer with ring-opening or, wherein the case of an ADMET polymerization, one or more linearα,ω-dieneyl-monomer are condensed with the loss of a small alkene, withthe polymer formed after combining the monomer with a Ruthenium-basedcatalyst and heating to a temperature greater than 100° C. Themetathesis can be a ring-closure reaction where an acyclicnon-conjugated diene self condenses in the presence of a Ruthenium-basedcatalyst when heated to a temperature above 100° C.

These and other features, aspects, and advantages of various embodimentswill become better understood with reference to the followingdescription, figures, and claims.

BRIEF DESCRIPTION OF THE FIGURES

Many aspects of this disclosure can be better understood with referenceto the following figures, in which:

FIG. 1: is an example according to various embodiments, illustrating aplot of weight average molecular weight dependence of unsaturatedpoly(octylene) on reaction time at 100° C. using a catalyst according toStructure A and a catalyst according to Structure B.

FIG. 2: is an example according to various embodiments, illustrating aplot of the weight average molecular weight (Mw) achieved forpoly(oct-4-ene-alt-sulfone) at different temperatures (° C.) ofpolymerization at both 5 and 40 hour reaction times using a catalystaccording to Structure A;

FIG. 3: is an example according to various embodiments, illustrating aplot of the weight average molecular weight (Mw) increase over a 100hour period for poly(oct-4-ene-alt-sulfone) polymerized at 150° C. forcatalyst loadings of 0.3 mole %, 0.5 mole %, and 1.0 mole %; and

FIG. 4: is an example according to various embodiments, illustrating adifferential scanning calorimetry (DSC) curve for thepoly(oct-4-ene-alt-sulfone) that was formed upon polymerization at 100and 150° C., with and without benzoquinone included with the catalyst.

It should be understood that the various embodiments are not limited tothe examples illustrated in the figures.

DETAILED DESCRIPTION

Various embodiments may be understood more readily by reference to thefollowing detailed description. Unless defined otherwise, all technicaland scientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which this disclosurebelongs. Although any methods and materials similar or equivalent tothose described herein can also be used in the practice or testing ofthe present disclosure, the preferred methods and materials are nowdescribed.

As used herein, the term “standard temperature and pressure” generallyrefers to 20° C. and 1 atmosphere. Standard temperature and pressure mayalso be referred to as “ambient conditions.” Unless indicated otherwise,parts are by weight, temperature is in ° C., and pressure is at or nearatmospheric. The terms “elevated temperatures” or “high-temperatures”generally refer to temperatures of at least 100° C.

The term “mol percent” or “mole percent” generally refers to thepercentage that the moles of a particular component are of the totalmoles that are in a mixture. The sum of the mole fractions for eachcomponent in a solution is equal to 1.

As used herein, the term “metathesis” generally refers to a reaction inwhich two compounds exchange ions, typically with precipitation of aninsoluble product.

It is to be understood that this disclosure is not limited to particularembodiments described, as such may, of course, vary. It is also to beunderstood that the terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting, since the scope of the present disclosure will be limited onlyby the appended claims.

All numeric values are herein assumed to be modified by the term“about,” whether or not explicitly indicated. The term “about” generallyrefers to a range of numbers that one of skill in the art would considerequivalent to the recited value (i.e., having the same function orresult). In many instances, the term “about” may include numbers thatare rounded to the nearest significant figure.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit (unlessthe context clearly dictates otherwise), between the upper and lowerlimit of that range, and any other stated or intervening value in thatstated range, is encompassed within the disclosure. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges and are also encompassed within the disclosure, subjectto any specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either orboth of those included limits are also included in the disclosure.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publication or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present disclosure is not entitled to antedate suchpublication by prior disclosure. Further, the dates of publicationprovided could be different from the actual publication dates that mayneed to be independently confirmed.

Unless otherwise indicated, the present disclosure is not limited toparticular materials, reagents, reaction materials, manufacturingprocesses, or the like, as such can vary. It is also to be understoodthat the terminology used herein is for purposes of describingparticular embodiments only and is not intended to be limiting. It isalso possible in the present disclosure that steps can be executed indifferent sequence where this is logically possible.

It must be noted that, as used in the specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the context clearly dictates otherwise. Thus, for example,reference to “a support” includes a plurality of supports. In thisspecification and in the claims that follow, reference will be made to anumber of terms that shall be defined to have the following meaningsunless a contrary intention is apparent.

Various embodiments are directed to methods of performing metathesischemistry at temperatures of at least 100° C. that may employ catalysts.For example, two schematic chemical structures of suitable rutheniumcatalysts, are illustrated shown in Structure A and in Structure B.

More specifically, Structure A is an example according to variousembodiments, illustrating a schematic chemical structure of a rutheniumcatalyst that may be used for high temperature metathesis chemistry.Structure B is an example according to various embodiments, illustratinga schematic chemical structure of a ruthenium catalyst that may be usedfor high temperature metathesis chemistry. The ruthenium catalystsillustrated in Structure A and in Structure B may be referred to asHoveyda-Grubb's type catalysts that contain asymmetric N-heterocycliccarbene ligands or cyclic(alkyl)(amino) carbene ligands. The catalystsare stable at ambient conditions for extended periods of time.

It has been discovered that other catalysts of similar structure mayalso be employed, differing in structure to those of Structure A andStructure B by the substitution on the aromatic rings, the alkyl groupof the alky aryl ether, and with ligands other than Cl⁻ can be employedas the thermally stable equivalent catalysts for metathesis reactions.For example, Structure C is an example according to various embodiments,illustrating a schematic chemical structure of a ruthenium catalyst thatmay be used for high temperature metathesis chemistry. Given certainselections of the functional groups (R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, and R₁₆), Structure C includes orencompasses both Structure A and Structure B.

The following lists provide some examples of the functional groups thatmay be employed in Structure C. The functional groups listed are merelyexamples; other functional groups may be employed. Referring toStructure C, functional groups R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,R₁₁, R₁₂, R₁₃, and R₁₄ may be the same or different and may each beindependently selected from hydrogen (H), a linear C₁-C₆ hydrocarbon, abranched C₃-C₆ hydrocarbon, and a cyclic C₃-C₆ hydrocarbon. Stillreferring to Structure C, functional groups R₁₅ and R₁₆ may be the sameor different and may each be any negative ligand. For example,functional groups R₁₅ and R₁₆ may be the same or different and may eachbe independently selected from Cl— (chloro), CN— (cyano), Br— (bromo),O— (oxo), OH— (hydroxo), CO₃— (carbonato), CH₃COO— (acetato), SCN—(thiocyanato), SO₄— (sulphato), C₂O₄— (oxalato), and NO₂— (nitrito). Inthis context, “independently selected” means that each group may bechosen from the list of options with out respect to the selection madefrom the list for any other groups, allowing the functional groups to bethe same or different.

Various embodiments are directed to methods of performing metathesischemistry at temperatures of at least 100° C.

Acyclic Diene Metathesis Polymerization (ADMET) Polymerization orCopolymerization

According to various embodiments, the high-temperature metathesispolymerization may be an ADMET polymerization or copolymerization, whereone or more non-conjugated acyclic diene has a boiling point in excessof 100° C. and a melting point (T_(m)) below the polymerizationtemperature.

The polymerization temperature may be in a range having a lower limitand/or an upper limit. The range may include or exclude the lower limitand/or the upper limit. The lower limit and/or upper limit can beselected from about 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130,140, 150, 160, 170, 180, 190, and 200° C. For example, according tocertain embodiments, the polymerization temperature may be in a range offrom about 20° C. to about 200° C., or any combination of lower limitsand upper limits described.

The catalyst concentration may be in a range having a lower limit and/oran upper limit. The range may include or exclude the lower limit and/orthe upper limit. The lower limit and/or upper limit can be selected fromabout 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85,0.9, 0.95, and 1 mol percent. For example, according to certainembodiments, the catalyst concentration may be in a range of from about0.3 to about 1 mol percent, or any combination of lower limits and upperlimits described.

The reaction time may be in a range having a lower limit and/or an upperlimit. The range may include or exclude the lower limit and/or the upperlimit. The lower limit and/or upper limit can be selected from about 5,10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,and 100 hrs. For example, according to certain embodiments, the reactiontime may be of from about 5 to about 100 hrs, or any combination oflower limits and upper limits described.

Polymerization or copolymerization may optionally be carried out in themelt. The polymerization or copolymerization may employ a catalyst asillustrated in Structure A, Structure B, or Structure C, or anequivalent thereof. The polymerization may be carried out in a solventhaving a boiling point greater than the temperature of polymerization.Although an advantage of various embodiments is the elimination ofsolvent, a solvent may be used. An example of a solvent that may be usedis propylene carbonate. The acyclic diene may be a functionalized dieneor an unfunctionalized diene, where any functionalization does notinhibit or poison the catalyst. If functionalization occurs too close tothe terminal olefin (less than 3 methylene spacers) coordination of thefunctional group with the catalyst could occur simultaneously orpreferentially with respect to the olefin. This will limitcatalyst/olefin reactivity and therefore polymer molecularweight/reaction progress. A functionalized diene may be functionalizedwith one or more functional groups. The functional groups may be,separately or in combination, alkyl, aryl, alkylaryl, ketone, aldehyde,ether, ester, carboxylic acid, alkylsilyl, arylsilyl, alkylarylsilyl,amine, epoxy, sulfone, sulfonic acid ester, amides, or any otherfunctional group. Hydrogenation may be performed in any suitable manner.

For example, an unsaturated polymer may be combined with 3 equiv ofp-toluenesulfonyl hydrazine (TSH) and tripropylamine (TPA) dissolved ino-xylene. After a bubbler is attached, the reaction mixture may berefluxed until nitrogen is no longer being evolved from the reactionvessel. After addition of more TSH and TPA, the mixture may be refluxeduntil no more nitrogen is released. The solvent may be removed, and thepolymer may be analyzed via 13C and 1H NMR to determine whether completesaturation was achieved

According to various other embodiments and examples, hydrogenation hasbeen performed using a 150 mL Parr high-pressure stainless steelreaction vessel equipped with a 50 mL round bottom flask and a Teflonstirring bar/0.15 g of unsaturated polymers may be dissolved in 20 mL ofanhydrous toluene and degassed for 1 hour before adding 15 wt % of Pd/C.The round bottom flask was placed into the bomb and then sealed. TheParr vessel was purged with 500 psi of hydrogen gas three times. Thebomb was then charged to 900 psi, and the mixture was stirred for 5 daysat 90° C. The resultant polymer was filtered and precipitated into coldmethanol to obtain a white solid, which was then filtered, transferredto a vial and dried under high vacuum (3×10−4 mmHg) overnight, yielding0.13 g (87%) of final polymer.

According to various embodiments high-temperature metathesispolymerization may be an ADMET polymerization or copolymerization mayproduce a polymer or a copolymer having a wide range of molecularweights. The polymers or copolymers may have a weight average (Mw)within a range having a lower limit and/or an upper limit. The range mayinclude or exclude the lower limit and/or the upper limit. The lowerlimit and/or upper limit can be selected from about 35, 40, 45, 50, 55,60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135,140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, and 200kg/mol. For example, according to certain embodiments, the polymers orcopolymers may have a weight average (Mw) of from about 35 to about 130kg/mol, or any combination of lower limits and upper limits described.

Ring-Opening Metathesis Polymerization (ROMP)

According to various embodiments, the high-temperature metathesispolymerization may be a ring-opening metathesis polymerization (ROMP) orcopolymerization carried out at temperatures in excess of 100° C. Afunctionalized or unfunctionalized cyclic olefin or alkene may have aboiling point in excess of 100° C. and a T_(m) below the polymerizationtemperature. Polymerization or copolymerization may optionally becarried out in the melt. The polymerization or copolymerization mayemploy a catalyst as illustrated in Structure A, Structure B, orStructure C, or an equivalent thereof. The polymerization can be carriedout in a solvent with a boiling point greater than the temperature ofpolymerization. The polymerization can be carried out to high molecularweights as long as functional groups on the cyclic olefin or alkene doesnot inhibit or poison the catalyst. The functional groups of the cyclicolefin or alkene may be, separately or in combination, alkyl, aryl,alkylaryl, ketone, aldehyde, ether, ester, carboxylic acid, alkylsilyl,arylsilyl, alkylarylsilyl, amine, epoxy, sulfone, sulfonic acid ester,amides, or any other functional group.

Ring-Closure Metathesis

According to various embodiments, the high-temperature metathesispolymerization may be a ring-closure metathesis can be carried out usingthe catalysts of Structure A, Structure B, Structure C, or theirequivalent. The ring-closure can be carried out at temperatures inexcess of 100° C. where a functionalized or unfunctionalizednon-conjugated diene has a boiling point in excess of 100° C. and aT_(m) below the metathesis reaction temperature. The reaction can becarried out in the melt for some dienes or carried out in solution andemploying a catalyst of Structure A, Structure B, Structure C, or theirequivalent. The metathesis reaction solvent should have a boiling pointgreater than the temperature of the reaction. Functional groups of afunctionalized non-conjugated diene can be, separately or incombination, alkyl, aryl, alkylaryl, ketone, aldehyde, ether, ester,carboxylic acid, alkylsilyl, arylsilyl, alkylarylsilyl, amine, epoxy,sulfone, sulfonic acid ester, amides, or any other functional group.

Olefin-Exchange Metathesis

According to various embodiments, the high-temperature metathesischemistry may be olefin-exchange metathesis can be carried out using thecatalysts of Structure A, Structure B, Structure C, or their equivalent.The exchange reaction can be carried out at temperatures in excess of100° C. where a functionalized or unfunctionalized ene, diene, triene orpolyene has a boiling point in excess of 100° C. and a T_(m) below themetathesis reaction temperature. The exchange can be driven to a singleproduct or a plurality of products depending upon the proportion ofreactant olefins, their relative concentration, their symmetry,volatility of an exchange product, or other factor. The functionalgroups can be, separately or in combination, alkyl, aryl, alkylaryl,ketone, aldehyde, ether, ester, carboxylic acid, alkylsilyl, arylsilyl,alkylarylsilyl, amine, epoxy, sulfone, sulfonic acid ester, amides, orany other functional group.

EXAMPLES

The following examples are put forth to provide those of ordinary skillin the art with a complete disclosure and description of how to performthe methods and use the compositions and compounds disclosed and claimedherein. Efforts have been made to ensure accuracy with respect tonumbers (e.g., amounts, temperature, etc.), but some errors anddeviations should be accounted for.

The purpose of the following examples is not to limit the scope of thevarious embodiments, but merely to provide examples illustratingspecific embodiments. Example 1 illustrates a reaction scheme for hightemperature polymerization of bis-pent-4-enesulfone to apoly(oct-4-ene-alt-sulfone) and its hydrogenation topoly(octyl-alt-sulfone). Example 2 illustrates a reaction scheme forhigh temperature polymerization of bis-pent-4-enesulfone to apoly(oct-4-ene-alt-sulfone) and its hydrogenation topoly(octyl-alt-sulfone).

Example 1

In an exemplary embodiment, the synthesis of poly(octylene) at 100° C.occurs, as shown Reaction Scheme 1, using a catalyst according toStructure A, Structure B, or Structure C. More specifically, ReactionScheme 1 is an example according to various embodiments, illustrating areaction scheme for high temperature polymerization of 1,9-decadiene topoly(octylene) and its hydrogenation to polyethylene.

The melting temperature of poly(octylene) is 30° C. by differentialscanning calorimetry (DSC). High molecular weight polymer was formed bythis step growth polymerization. The poly(octylene) can be converted topolyethylene by hydrogenation, where the melting temperature of theresulting polyethylene is approximately 130° C. The melting temperatureindicates that no branching occurs during the polymerization.

FIG. 1 is a plot of weight average molecular weight dependence ofunsaturated poly(octylene) on reaction time at 100° C. using a catalystaccording to Structure A and a catalyst according to Structure B.

Data from FIG. 1 is summarized in Table 1.

TABLE 1 Catalyst Structure A Catalyst Structure B Time (hrs) Mw (g/mol)Time (hrs) Mw (g/mol) 5 43000 5 36000 20 51500 24 33000 40 64000 5244000 93 63000 96 39000

Example 2

The synthesis of a sulfone monomer, was carried out as is known in theprior art, for example as disclosed in Gaines et al. Reaction Scheme 2is an example according to various embodiments, illustrating a reactionscheme for high temperature polymerization of bis-pent-4-enesulfone to apoly(oct-4-ene-alt-sulfone) and its hydrogenation topoly(octyl-alt-sulfone).

The solid monomer was heated above its melting temperature of 40° C. anddegassed. Polymerizations were performed at various reactiontemperatures, times, and with various catalyst levels.

FIG. 2 is an example according to various embodiments, illustrating aplot of the weight average molecular weight (Mw) achieved forpoly(oct-4-ene-alt-sulfone) at different temperatures (° C.) ofpolymerization. FIG. 2 shows a clear dependence of molecular weight withpolymerization temperature. Polymerizations performed below the T_(m) ofthe unsaturated polysulfone achieved a molecular weight (MW) on theorder of 15 kg/mol. The MW doubled upon raising the polymerizationtemperature above the T_(m). The increase in MW was attributed toincreased polymer chain-end diffusion due to removing constraintsimposed by formation of crystalline domains. FIG. 2 displays the MW ofpolymers formed using a reaction time of 40 hours. The dependence of MWon temperature being above T_(m) occurs even when reaction times arelonger. Data from FIG. 2 is summarized in Table 2.

TABLE 2 5 hr reaction time 40 hr reaction time Temp (□ C.) Mw (g/mol)Temp (□ C.) Mw (g/mol) 110 15283 100 12644 120 14368 150 36458 140 35512165 35498 150 36544 175 39608 165 57489 200 19123 175 58452 200 30754

FIG. 3 is an example according to various embodiments, illustrating aplot of the weight average molecular weight (Mw) increase over a 100hour period for poly(oct-4-ene-alt-sulfone) polymerized at 150° C. forcatalyst loadings of 0.3 mole %, 0.5 mole %, and 1.0 mole %. FIG. 3shows the polysulfone's molecular weight dependence on polymerizationtime and catalyst concentration. Molecular weight increases withincreasing reaction time and greater catalyst concentrations forcatalyst concentrations of 0.3 to 1.0 mol %; which is typical ofcatalyst concentrations used for ADMET polymerizations. Inefficientstirring due to the highly viscous polymer melts impedes formation ofhigh MW. The results of FIG. 2 and FIG. 3 were achieved with magneticstirring, and superior rates are expected from other modes of agitation.The data from FIG. 3 is summarized in Table 3.

TABLE 3 0.33 mol % catalyst 0.50 mol % catalyst 1.0 mol % catalyst TimeMw Time Mw Time Mw (hrs) (g/mol) hrs (g/mol) (hrs) (g/mol) 5 34859 536458 5 48017 42 26448 43 36544 40 87162 90 58624 70 66207 93 132187 9063962

The aliphatic polysulfones show a melting temperature dependence on thepolymerization temperature. Increased reaction temperatures prompted adecrease in the melting temperature of a saturated polymer formed uponhydrogenation. Polymerizations performed at 100° C. resulted insaturated polysulfones upon hydrogenation that display a T_(m) of 180°C. When the polymerization temperature was raised to 150° C., thesaturated polymer T_(m) decreases to 155° C. The decrease in meltingtemperature is consistent with olefin isomerization of the monomer athigher temperatures, leading to various methylene spacing betweensulfone groups of the resulting saturated copolymer. The optionaladdition of benzoquinone additives at 2-4 mol % of the diene monomer maybe employed to suppress olefin isomerization. The saturatedpolysulfone's T_(m) at 150° C. polymerization temperature was similar tothat of the 100° C. polymerization in the absence of the benzoquinone.

FIG. 4 is an example according to various embodiments, illustrating adifferential scanning calorimetry (DSC) curve for thepoly(oct-4-ene-alt-sulfone) that was formed upon polymerization at 100and 150° C., with and without benzoquinone included with the catalyst.FIG. 4 shows DSC results for the polysulfones polymerized at 100 and150° C., with and without benzoquinone. The addition of benzoquinone at100° C. polymerization temperature had only a small effect on thesaturated polymers' melting temperatures (T_(m)), which is consistentwith little or no isomerization occurring at 100° C. polymerizationtemperatures, whereas at 150° C. in the absence of benzoquinone,significant isomerization appears to occur.

All the features disclosed in this specification (including anyaccompanying claims, abstract, and drawings) may be replaced byalternative features serving the same, equivalent or similar purpose,unless expressly stated otherwise. Thus, unless expressly statedotherwise, each feature disclosed is one example only of a genericseries of equivalent or similar features.

Any element in a claim that does not explicitly state “means for”performing a specified function, or “step for” performing a specificfunction, is not to be interpreted as a “means” or “step” clause asspecified in 35 U.S.C § 112, sixth paragraph. In particular, the use of“step of” in the claims herein is not intended to invoke the provisionsof 35 U.S.C § 112, sixth paragraph.

All patents, patent applications, provisional applications, andpublications referred to or cited herein, supra or infra, areincorporated by reference in their entirety, including all figures andtables, to the extent they are not inconsistent with the explicitteachings of this specification.

It should be emphasized that the above-described embodiments of thepresent disclosure are merely possible examples of implementations andare merely set forth for a clear understanding of the principles of thisdisclosure. It should be understood that the examples and embodimentsdescribed herein are for illustrative purposes only and that variousmodifications or changes in light thereof will be suggested to personsskilled in the art and are to be included within the spirit and purviewof this application. Many variations and modifications may be made tothe above-described embodiment(s) of the disclosure without departingsubstantially from the spirit and principles of the disclosure. All suchmodifications and variations are intended to be included herein withinthe scope of this disclosure and protected by the following claims.

What is claimed is:
 1. A method of metathesis polymerization, comprising: forming a polymerization mixture by combining a Ruthenium-based catalyst comprising a cyclic(alkyl)(amino) carbene ligand, a quinone, and one or more monomers selected from at least one cyclic monomer comprising an alkene, at least one linear monomer comprising an α,ω-dieneyl-monomer, and combinations thereof; heating the polymerization mixture to a temperature of 100° C. or greater.
 2. The method of metathesis polymerization according to claim 1, wherein the monomer comprises a functional group selected from alkyl, aryl, alkylaryl, ketone, aldehyde, ether, ester, carboxylic acid, alkylsilyl, arylsilyl, alkylarylsilyl, amine, epoxy, sulfone, sulfonic acid ester, and amides.
 3. The method of metathesis polymerization according to claim 1, wherein the temperature is 120° C. or greater.
 4. The method of metathesis polymerization according to claim 1, wherein the quinone is benzoquinone.
 5. The method of metathesis polymerization according to claim 1, wherein the polymerization mixture further comprises a solvent having a boiling point in excess of the polymerization temperature at the polymerization pressure.
 6. The method of metathesis polymerization according to claim 1, wherein the catalyst is: 